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IC-302 Unit -2C Dr. N. K.

Patel 

Natubhai V. Patel College of Pure & Applied Sciences
T. Y. B.Sc. (Industrial chemistry)
IC – 302: Unit Process, Synthetic dyes and Pharmaceuticals
UNIT – 2C
Syllabus

Esterification: Introduction, mechanism and commercial manufacturing of Ethyl acetate and
Vinyl acetate.

ESTERIFICATION

2.13 INTRODUCTION

An ester is usually defined as a compound formed by substituting a group
such as ethyl (-C2H5) for the ioniable H of an acid. In many instances it is probably
more accurate to regard it as an alcohol of which the hydroxyl H has been replaced by
the acyl group.

2.14 ESTERIFICATION BY ORGANIC ACIDS

An ester is usually defines as a compound formed by substituting an organic radical
for an ionizable hydrogen of an acid.
The mechanism by which this replacement occurs has been well established. If the
direct esterification of an acid, such as acetic, by an alcohol, such as ethanol, is considered,
the possibility of breaking either the carbonyl oxygen bond or the alkyl-oxygen bond is
evident.

Evidence for the breaking of the carbonyl-oxygen bond was found in the study of the
following reaction.

In which water was formed. If the alkyl-sulfur bond had broken, hydrogen sulfide
would have been formed. That the carbonyl-oxygen bond is the one broken was confirmed
by the finding that esterification of benzoic acid containing the normal oxygen isotope
distribution by methanol enriched with O18 produced methyl benzoate containing the heavy
oxygen isotope, while the water formed had only the normal isotope distribution. A
generalized explanation for the selectivity of the bond-breaking process is found in the
electronic structure of the reactants and products. Since oxygen is more electronegative
than carbon, the carbonyl carbon is more positive than the carbonyl oxygen. This may be
represented as:

Any compound (B) containing a free pair of electrons, whether due to ionization or
not, can attack this positive center. Thus,

1

is reached. Esterification catalysts are compounds. The secondary alcohols are markedly lower than the primary in both initial velocity and limit but vary considerably among them. which originally attacked the positive center. Allyl alcohol is much slower than propyl. The tertiary alcohols show little esterification in 1 hr and hardly any more in 100. Phenol and thymol. The esterification reactions are reversible and that the extent of reaction depended on the relative amounts of each compound present. the limit is seldom if ever reliable. IC-302 Unit -2C Dr. The neutralization reaction of such an acid is written as the donation of an electron pair by a base to the acid. secondary. both as to the rates and as to the limits of esterification. heating alone does not speed up esterification to a practical rate. As was discussed earlier. the saturated alcohol with the same number of carbon atoms. the more rapid the reaction will be. propyl. Like most other reactions. However. In the case of the tertiary alcohols. since these alcohols are dehydrated easily to the unsaturated hydrocarbon and the acid. The primary alcohol ethyl. show low initial rated but comparatively high limits. and tertiary alcohols. or limit. which may be regarded as tertiary alcohols but from which water cannot be split off. Equilibrium will be established between the starting materials and the final products since the hydroxyl ion produced can attack III to form the same transition state as that from I and II. esterification proceeds by attack of an alcohol molecule on the slightly positive carbonyl carbon of an acid. or zinc chloride can be considered to be acids. which are acidic in nature. heat is used to speed up esterification reactions. and butyl have approximately the same initial rates and limits but are inferior to methyl alcohol in both of these respects. such as glycerol. such as sulfuric or hydrochloric acid. 2 . K. but days and even months will elapse before the minimum value. other methods or catalysts can be used to increase the positive charge so that a given acid will esterifies more rapidly. a slow decrease in acidity can be observed. with high boiling acid such as stearic. It has long been known that the process of esterification may be enormously hastened by the addition of a strong acid. While the nature of the R group attached to the carbonyl group will influence this charge.15 CATALYTIC ESTERIFICATION If samples are taken at intervals from a mixture of acetic acid arid ethyl alcohol at room temperature and titrated. N. Patel  The transition state can lose the negative charge by loss either of a hydroxyl ion or of the species. Menschutkin made a comparative study of the relative rates of esterification and the equilibrium constant of a large number of acids and alcohols. in most instances. compounds such as boron trifluoride. The presence of the phenyl group in benzyl alcohol has a retarding influence. Acidic compounds in this case are those in which the central atom has an incomplete external electron shell. esterification cannot be affected at atmospheric pressure in reasonable time without the use of catalyst. The equilibrium constant for the reaction is Unless activities are used in this expression. the value of K changes with the presence of salts. so that besides the hydrogen ion. except in the case of a high- boiling alcohol. 2. the speed of esterification approximately doubles with 100C rise in temperature. it is not unusual with esters of tertiary alcohols. aluminum chloride. Hence. He found striking differences among primary. only the rate of esterification is increased. to find less ester present after a long heating period than after a short one. The equilibrium point of the reaction is not altered by the catalyst. The larger this positive charge.

the esterification is self-catalyzed. in addition. N. 2.2 Thermodynamics of Alcoholysis Alcoholysis may be regarded as a special case of esterification. K. The mechanism may be written two ways. Quite often the speed of the reaction is increased by working under increased pressure so that higher temperatures can be used. CH3COOC2H5 + HOCH3 CH3COOCH3 + HOC2H5 (1) 2. this reaction hinders esterification and. The alcoholysis equilibrium (K) can be calculated from the respective esterification constants (K1 and K2) of methanol and ethanol with benzoic acid. if 1 mole of methanol is added to 1 mole 3 . we have This relationship between the esterification constants is as true in the absence of water and free acid as it is in their presence. Thus. may be written for alcoholysis reactions. Attention should be called to the fact that the alcohol oxygen also can act as a base toward the acid. which is similar to those for the esterification of acids by alcohols. Patel  When an acid (HA) is added to an esterification mixture. C6H5COOH + CH3OH C6H5COOCH3 + H2O K1(C6H5COOH)(CH3OH) = (C6H5COOCH3)(H2O) (2) C6H5COOH + C2H5OH C6H5COOC2H5 + H2O K2(C6H5COOH)(C2H5OHOH) = (C6H5COOC2H5)(H2O) (3) By dividing equation (2) by equation (3).16. Equilibrium expression. However. In certain cases when the acid is sufficiently strong. the oxygen present will act as bases and coordinate with the acid. IC-302 Unit -2C Dr. may lead to dehydration of the alcohol / dehydration is an especially important side reaction with tertiary alcohols. depending on which oxygen of the carbonyl group acts as the base.16 ESTERIFICATION OF CARBOXYLIC ACID DERIVATIVES 2.1 Alcoholysis In the alcoholysis or ester-interchange reaction.16. an alcohol reacts with as ester to give a new ester.

They are effective in catalyzing interchange between two esters as well as between an alcohol and an ester. zinc is used as the catalyst. The most commonly used catalysts for alcoholysis. The greater rapidity of alcoholysis compared with hydrolysis may be shown qualitatively by a simple experiment with triacetin. They must be used in anhydrous systems since they are hydrolyzed by water and the resulting hydroxides hydrolyze the esters. Patel  of ethyl benzoate. IC-302 Unit -2C Dr. The sodium methoxide-catalyzed methanolysis of 1-methyl benzoate is first order with respect to both ester and methoxide ion and does not involve fission of the alkyl-to-oxygen bond. They usually do not catalyze side reactions. Low concentrations of these catalysts cause the transformation to take place rapidly even at room temperature. Since the alcoholysis equilibrium is related to the esterification constant of the alcohols with the acid a tertiary alcohol will not replace a primary alcohol in alcoholysis. An acid might polymerize the unsaturated alcohol. At room temperature in the absence of a catalyst. sodium hydroxide and sodium carbonate. The remarkable quality of alcoholysis in the presence of sodium ethoxide as catalyst is the rapidity of reaction as compared with esterification and saponification. 0. are the sodium alkoxides. K. The evidence indicates that the mechanisms of basic ester interchange and basic ester hydrolysis are similar. The usual practice is to dissolve a small amount of sodium in the alcohol to be used and then to add the ester. Then the ethyl benzoate is saponified slowly. it is necessary to use an efficient reflux condenser when determining saponification numbers of even high-boiling acetates. while sodium methoxide would react with the halogen of the acid. Besides the sodium alkoxides. tetramethylammonium hydroxide.53 mole of the methyl ester will be formed and like amount of ethyl alcohol set free. On this account. equilibrium is established extremely slowly. various other catalysts for this reaction have been recommended: ammonia. N. is added to a solution of sodium hydroxide in 50 % alcohol the odor of ethyl acetate is apparent at once and shows that the immediate reaction is the information of ethyl acetate. In the alcoholysis of ethyl esters of alpha-halogenated acids by allyl and methallyl alcohols. 4 . pyridine. Sodium ethoxide is about one thousand times as active as an equivalent amount of hydrochloric acid. An explanation for this increase in rate is that the basicity of the alcohol oxygen is increased and that this increase in basicity facilitates attack on the positive carbonyl carbon. and they are especially useful with polymerizable standard ester-exchange catalysts. lithium methoxide. however. The strong acids that are used as catalysts in ordinary esterification serve equally well for alcoholysis. aluminum alkoxides. The mechanism of acid-catalyzed alcoholysis is similar to that of acid-catalyzed esterification. Some triacetin C3H5 (OCOCH3)3 which Is odourless. The saponification of phenyl benzoate in aqueous alcohol ordinarily would be represented by equation 4 C6H5COOC6H5 + NaOH C6H5COONa + C6H5OH (4) C2H5OH + NaOH C2H5CONa + H2O (5) C6H5COOC6H5 + NaOC2H5 C6H5COOC2H5 + C6H5ONa (6) What actually takes place is the alcoholysis represented in equations 5 and 6 which was estimated by Gibby and Water’s to be one thousand limes as rapid as the saponification according to equation (1). and a secondary alcohol will replace a primary alcohol to a small extent only. Titanium esters are excellent ester-exchange catalysts.

triethylamine. since all the ketene goes into the product and there are no by-products. 5 . a vinyl ester or an ester of ethylidene glycol is formed according to reaction. K. the method provides a convenient way of introducing hydroxyl groups into hydrocarbons. IC-302 Unit -2C Dr. Esters are produced by the reaction of ketene with an acetal or ortho ester. Even t-butyl alcohol reacts readily with ketene in the presence of sulfuric acid.2 Ester from Acetylene When acetylene and acetic acid are brought together with a suitable catalyst. Other catalysts. Zinc salts of aliphatic acids on carbon carriers are excellent catalysts for the vapor-phase reaction. 2. which is used for making polymers.17. N. particularly with some of the terpenes. Vinyl acetate. which is an intermediate for the manufacture of acetic anhydride. CH2 = C = O + C2H5OH CH3COOC2H5 Ketene is an effective acetylating agent as acetic anhydride. to avoid the polymerizing effects of sulfuric acid. They may be used in conjunction with mercury salts. 2. The addition may be effected in the vapor phase over a solid catalyst at 200°C or above.3 Esterification by Ketene The reaction of ketene with alcohols to produce esters is attractive. but goes well with many of the higher alkenes. Strong acids. zinc acetate. Boron trifluoride is an excellent catalyst for the addition. Since the formates are easily hydrolyzed. The addition of formic acid to olefin is easily controlled and gives high yields of esters. Patel  2. heteropoly acids. or metal phosphates. include boron trifluoride and the salts of various metals. Salicylic acid is acetylated by ketene. The addition of carboxylic acids to the double bonds of isobutylene and trimethyl ethylene gives tertiary esters. and phosphoric acids are catalysts.17.17 ESTERS BY ADDITIONS TO UNSATURATED SYSTEMS 2. A catalyst is often necessary to complete the reaction. A true equilibrium independent of sulfuric acid concentration is established in the exothermic reaction. The addition may take place at room temperature or higher and is aided by pressure. which have been disclosed for the reaction. methane di-and trisulfonic. is produced on a large scale.17. The reaction may be applied to other carboxylic acids and acetylene derivatives.1 Addition of an Acid to an Olefin The addition of an organic acid to an unsaturated hydrocarbon in the presence of a strong-acid catalyst probably occurs through an Intermediate carbonium ion The addition takes place according to Markownikoff’s rule. such as zinc silicate. such as sulfonic acids. The addition does not go well with ethylene. various other catalysts. The vapors of the acid and hydrocarbon may be passed over catalysts. hydrofluoric acid. Hg(OCOCH3)2 + CH3COOH CH3CCOOCH=CH2 Hg(OCOCH3)2 + 2CH3COOH CH3CH(OCOCH3)2 By altering the reaction conditions. and mercuric phosphate. Zinc acetate is widely used in the manufacture of vinyl acetate. boron trifluoride and cuprous chloride have been used. and ethylidene diacetate. a preponderance of either product may be produced as desired. such as sulfuric. Zinc salts may be used also as catalysts for the preparation of vinyl esters of higher carboxylic acids in the liquid phase. such as activated carbon.

IC-302 Unit -2C Dr. Zinc acetate as catalyst 2. as is illustrated in the flow diagram. Patel  2. Resin formation during distillation is prevented by the addition of thiodiphenylamine to the crude vinyl acetate in the still. acetic acid.1 Raw materials Acetylene. is collected in a column line which flows to the still. is preferably carried out as a vapor-phase reaction between acetylene and acetic acid. A suitable catalyst consists of 3-5 mm granules of a mixture of 42parts of zinc acetate to 100parts of activated charcoal. The yield of vinyl acetate varies from 92 – 95 % based on acetylene and from 97 – 99 % based on acetic acid. The best economic balance is obtained at a conversion of 60%. is provided by horizontal steel tubes in the catalyst bed through which water is passed. A flow sheet showing the major items of equipment for a vapor-phase process is shown in figure. flows into the catalyzer in which the gas temperature is held at 170°C. The crude vinyl acetate vapor emerging from the catalyzer passes through the heat exchanger and then to a separator where carbon dusts is removed. Purified acetylene.2 Manufacture The manufacture of vinyl acetate. Zinc acetate is used commonly as the catalyst for these vapor-phase processed. 6 . The gas. which is heated to 1700C by passing through a series of heat exchangers and heaters. Condensate from each of these units. N. The rate of flow is adjusted so that the gas leaving the vaporizer carries with it 23 % by weight of acetic acid. to be used for preparing polyvinyl acetate.18 VINYL ACETATE 2. The vapor is then passed through a series of three condensers. The condensate averages 60% of pure vinyl acetate and 40% of acetic acid. K. The catalyzers are steel boxes in which the catalyst is held between vertical plates spaced 1 inch apart cooling of exothermic reaction. from which all traces of hydrogen sulfide and phosphine have been removed by scrubbing with sulfuric acid and passing over potassium dichromate and kieselguhr is bubbles through acetic acid heated to 60°C in the vaporizer.18. A charge of catalyst has a life of about two months when vinyl acetate is produced at a rate of 400-500 metric tons per month. The conversion to vinyl acetate in the catalyzer may be regulated either by adjusting the rate of gas flow through the catalyzer or by varying the reaction temperature.18. plus the liquid from the mist remover.

whence. In the process residual acid water. exhausted of its acid and the alcohol to as low a point of economical. N.19. 10% water and 70% alcohol. The dry ethyl acetate that accumulates in the calandria of the drying column is taken off through a cooler to the receiving tank (G). The washed ester. IC-302 Unit -2C Dr. the alcohol is exhausted and distills upward as vapor. The raw materials are first blended in a correct proportions and feed from the feed tank in a steady stream through a pre-heater into the esterifying column. The working up of crude ester made by the batch process is very similar to that employed in the continuous process. Another advantage is that the final purification and work up of the wash water can be tied in with the production of crude ester. These are setting out in the separator tank. while the slop water goes to waste at (E). K. The ternary mixture taken off passes to the separating column at point (B). blended with the alcohol and water accumulating in the base of the column. because it may contain salts of copper and higher-boiling esters formed from other acids present as impurities in the crude acetic acid employed. this ester. but in the former. and the take-off goes to a proportional mixing device. while a suitable amount of same distillate is refluxed back to the column at (A). From the top of the column is taken off a mixture of about 20% ester.1 Raw materials Acetic acid. In general.19 ETHYL ACETATE 2. needs to be redistilled before it can be placed on the market.19. Part of the condensate is returned as reflux to the top of the column. the watery portion overflowing back to the lower part of the separating column. Here it is rectified by closed steam in the calandria (C). is promptly and continuously discharged from the apparatus. the watery portion is passed by pipe (D) to a point in the esterification column.2 Manufacture A continuous process for making ethyl acetate. overflows from the separator at (F) and enters the drying column in which a sufficient amount is distilled off to came with it the water and alcohol. a special still must be provided for working up the weak wash waters unless this is done in the main batch still between esterification charges 7 . ethanol 2. although dry and holding very litter alcohol and free acid. containing a little dissolved water and alcohol. which may go either to the separating column of back to the mixer washer. which causes a separation into two layers. which is especially adapted to the utilization of dilute acetic acid as shown in flow diagram. The regulation of still is thus practically fixed. where it is blended with about an equal volume of water. and separator. On the lower plates the column. Patel  2.